WO2018109718A1 - Matériaux de silice modifiés de nouvelle génération pour des performances catalytiques accrues et des applications industrielles - Google Patents

Matériaux de silice modifiés de nouvelle génération pour des performances catalytiques accrues et des applications industrielles Download PDF

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WO2018109718A1
WO2018109718A1 PCT/IB2017/057956 IB2017057956W WO2018109718A1 WO 2018109718 A1 WO2018109718 A1 WO 2018109718A1 IB 2017057956 W IB2017057956 W IB 2017057956W WO 2018109718 A1 WO2018109718 A1 WO 2018109718A1
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silica
catalyst
alkaline earth
earth metal
heterostructured
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PCT/IB2017/057956
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English (en)
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Muhammad H. HAIDER
Toseef Ahmed
Khalid Karim
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Sabic Global Technologies B.V.
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Priority to US16/466,898 priority Critical patent/US11389784B2/en
Publication of WO2018109718A1 publication Critical patent/WO2018109718A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/88—Ferrosilicates; Ferroaluminosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron

Definitions

  • the present invention relates to heterostructured silica catalysts and uses thereof. More specifically, the present invention relates to heterostructured silica catalysts including a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • Silica containing materials play a pivotal role in many scientific industries including refining, petrochemical, specialty chemicals, biochemical, etc. This is due in part to a range of unique properties found in silica including high surface area, chemical, thermal, and mechanical stabilities, uniformly ordered pore distribution assisting substrate diffusion, and high adsorption tendencies. These properties of silica materials can vary based on the precursors used in their preparation, such as choosing between sodium silicate and a tetraalkyl orthosilicate, or by manipulating synthesis parameters including pH, temperature, reaction duration, additives in the reaction mixture, degree of condensation of poly silica etc.
  • Liu et al (“Calcein-functionalized Fe304@Si02 nanoparticles as a reusable fluorescent nanoprobe for copper(II) ion", Microchim Acta, 2015, 182, pp. 547-555) describes the preparation of silica supported Fe 3 0 4 nanoparticles for nanoprobes.
  • Silica sols can be used to make silica supports for catalysts and other materials. These silica-based supports suffer in that they have the catalytically active metals deposited in the pores of the silica support, deposited on the surface of the support, and/or unevenly distributed in the silica matrix.
  • the discovery is premised on forming heterostructured silica catalysts having a uniform single crystal structure with silicon (Si), catalytically active metal, and an alkaline earth metal oxide each present in the crystal lattice structure.
  • the catalysts of the present invention can be referred to as MHH-SiCh (i.e., Modified Haider Heterostructured S1O2) catalysts or materials.
  • the MHH-SiC catalysts of the present invention obtain their uniform single crystal structure by first forming a polycondensed silica having an external network of alkaline earth metal atoms (e.g., magnesium (Mg)) from a silicon containing organic template (e.g., tetraalkyl orthosilicate). Once formed, a catalytically active transition metal(s) (e.g., iron (Fe)) can be deposited the polycondensed silica structure.
  • a catalytically active transition metal(s) e.g., iron (Fe)
  • the active metal(s) migrates to the support center in a systematic pattern to obtain a uniform and uniquely structured MHH-Si02 material.
  • the catalytically active metal, silicon (Si), and an alkaline earth metal atom are each present in the crystal lattice structure.
  • Non-limiting advantages of the MHH-Si02 materials of the present invention include uniform surface morphology and high stability at increased temperatures over long durations. Further, the MHH-Si02 materials/catalysts of the present invention can avoid the issues seen with conventional silica-based materials such as having catalytically active metals deposited in the pores of the silica and/or unevenly distributed in the silica matrix.
  • the materials of the present invention can have applications in a wide variety of industries, including, for example, the chemical industry (e.g., catalyst for chemical reactions such as, but not limited to, a hydrogenation of carbon monoxide reaction).
  • the chemical industry e.g., catalyst for chemical reactions such as, but not limited to, a hydrogenation of carbon monoxide reaction.
  • Embodiments of the present invention describe a heterostructured silica catalyst.
  • the heterostructured silica catalyst can include a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • the catalyst can be monometallic, bimetallic, trimetallic, or tetrametallic.
  • the heterostructured silica catalyst can include 0.1 to 10 wt. % of the transition metal, 10 to 20 wt.% of the alkaline earth metal from the metal oxide thereof, and 20 to 40 wt. % of silicon (Si) from silica, based on the total weight of the catalyst.
  • the heterostructured silica includes a weight ratio of silicon (Si) from silica to alkaline earth metal from the metal oxide thereof that is from 0.5: 1 to 5: 1, preferably from 1 : 1 to 3 : 1.
  • the transition metal can be one or more of iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), zirconium (Zr), or titanium (Ti), preferably Fe.
  • the alkaline earth metal oxide can be one or more of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), or strontium (SrO), preferably magnesium oxide (MgO).
  • the method can include: (a) subjecting an aqueous solution comprising an alkaline earth metal precursor and a tetraalkyl orthosilicate to conditions sufficient to form a polycondensed silica having an external network of alkali earth metal atoms; (b) adding a transition metal precursor material to the aqueous solution under conditions to incorporate transition metal atoms into the polycondensed silica; (c) forming a solid material from the polycondensed silica; and (d) drying and calcining the solid material to form a heterostructured silica catalyst comprising a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • the aqueous solution from step (a) can include from 10 to 100 % water.
  • the aqueous solution from step (a) can include an alcohol, preferably ethanol, propanol, or butanol.
  • step (a) can include forming an alkaline earth metal precursor solution, heating the solution to a temperature ranging from room temperature (i.e., about 15 to about 30 °C, preferably about 20 to 25 °C) to 95 °C, preferably from 40 to 70 °C, and then adding tetraalkyl orthosilicate to the solution.
  • the molar ratio of tetraalkyl orthosilicate to alkaline earth metal precursor can be 0.5: 1 to 6: 1, preferably 1 : 1 to 4: 1.
  • the tetraalkyl orthosilicate is tetraethyl orthosilicate (TEOS).
  • the molar ratio of alkaline earth metal precursor to transition metal precursor from step (b) can be 5: 1 to 50: 1, preferably 20: 1 to 30: 1.
  • the solid material from step (c) can be obtained by adding a precipitating agent, wherein the precipitating agent is one or more of ammonium hydroxide (NH 4 OH), ammonium carbonate [(TNIH 4 ) 2 C0 3 ], ammonium bicarbonate ( H4HCO3), sodium carbonate (Na2CCb), potassium carbonate (K2CO3), sodium bicarbonate (NaHCCb), or potassium bicarbonate (KHCO3), preferably NH 4 OH.
  • the precipitating agent has a concentration from 1M to 10M of precipitation agent in water.
  • Another feature of the current invention involves calcination of the hetero structured silica catalyst and the calcination from step (d) can include heating at a temperature from 250 to 800 °C.
  • Another embodiment concerns a method of using the heterostructured silica catalyst of the present invention in a chemical reaction, such as in a hydrogenation of carbon monoxide reaction.
  • the reaction can include: 0.1 to 5 grams of the heterostructured silica catalyst; a feed stream comprising synthesis gas (CO/H2) at a weight hourly space velocity (WHSV) of 1000 to 2500; a temperature of 200 to 500 °C; and/or a pressure of 0 to 15 bar.
  • the method can also include producing a product stream that can include methane, olefins, paraffins, and/or carbon dioxide.
  • the carbon monoxide conversion can be 70 to 78% at 300 °C, 67 to 80% at 325 °C, and 14 to 53 %> at 350 °C.
  • the selectivity of methane can be 11 to 28%, the selectivity of olefins can be 24 to 41%), the selectivity of paraffins can be 13 to 21%>, and the selectivity of carbon dioxide can be 13 to 41%>, based on a reaction mass balance of 95 ⁇ 5%>.
  • Catalyst means a substance which alters the rate of a chemical reaction.
  • Catalytic or “catalytically active” means having the properties of a catalyst.
  • the term “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%. [0014] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the catalysts of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the catalysts of the present invention are a heterostructured material having a catalytically active metal, silicon (Si), and an alkaline earth metal each present in the crystal lattice structure of the catalyst.
  • Embodiment 1 is a heterostructured silica catalyst.
  • the heterostructured silica catalyst includes a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • Embodiment 2 is the heterostructured silica catalyst of embodiment 1, containing 0.1 to 10 wt. % of the transition metal, 10 to 20 wt.% of the alkaline earth metal from the metal oxide thereof, and 20 to 40 wt. % of silicon (Si) from silica, based on the total weight of the catalyst.
  • Embodiment 3 is the heterostructured silica catalyst of any of embodiments 1 to 2, wherein the weight ratio of silicon (Si) from silica to alkaline earth metal from the metal oxide thereof is from 0.5: 1 to 5: 1, preferably from 1 : 1 to 3 : 1.
  • Embodiment 4 is the heterostructured silica catalyst of any of embodiments 1 to 3, wherein the transition metal is one or more of iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), zirconium (Zr), or titanium (Ti), preferably Fe.
  • Embodiment 5 is the heterostructured silica catalyst of any of embodiments 1 to 4, wherein the alkaline earth metal oxide is one or more of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), or strontium (SrO), and preferably magnesium oxide (MgO).
  • the alkaline earth metal oxide is one or more of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), or strontium (SrO), and preferably magnesium oxide (MgO).
  • Embodiment 6 is a method of preparing a heterostructured silica catalyst.
  • the method of preparing a heterostructured silica catalyst includes the steps of (a) subjecting an aqueous solution containing an alkaline earth metal precursor and an tetraalkyl orthosilicate to conditions sufficient to form a polycondensed silica having an external network of alkali earth metal atoms; (b) adding a transition metal precursor material to the aqueous solution under conditions to incorporate transition metal atoms into the polycondensed silica; (c) forming a solid material from the polycondensed silica; and (d) drying and calcining the solid material to form a heterostructured silica catalyst containing a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • Embodiment 7 is the method of embodiment 6, wherein the aqueous solution from step (a) contains from 10 to 100 % water.
  • Embodiment 8 is the method of any of embodiments 6 to 7, wherein the aqueous solution from step (a) contains an alcohol, preferably ethanol, propanol, or butanol.
  • Embodiment 9 is the method of any of embodiments 6 to 8, wherein step (a) includes forming an alkaline earth metal precursor solution; heating the solution to a temperature ranging from 15 °C to 95 °C, preferably from 40 °C to 70 °C; and adding tetraalkyl orthosilicate to the solution.
  • Embodiment 10 is the method of embodiment 9, wherein the molar ratio of tetraalkyl orthosilicate to alkaline earth metal precursor is 0.5: 1 to 6: 1, preferably 1 : 1 to 4: 1.
  • Embodiment 11 is the method of embodiment 10, wherein the tetraalkyl orthosilicate is tetraethyl orthosilicate (TEOS).
  • Embodiment 12 is the method of any of embodiments 6 to 11, wherein the molar ratio of alkaline earth metal precursor to transition metal precursor from step (b) is 5: 1 to 50: 1.
  • Embodiment 13 is the method of embodiment 12, wherein the molar ratio is 20: 1 to 30: 1.
  • Embodiment 14 is the method of any of embodiments 6 to 13, wherein the solid material from step (c) is obtained by adding a precipitating agent, wherein the precipitating agent is one or more of ammonium hydroxide ( H4OH), ammonium carbonate [(NH 4 ) 2 C0 3 ], ammonium bicarbonate ( H4HCO3), sodium carbonate (Na 2 C0 3 ), potassium carbonate (K2CO3), sodium bicarbonate (NaHCCb), or potassium bicarbonate (KHCO3), preferably H4OH.
  • Embodiment 15 is the method of embodiment 14, wherein the precipitating agent has a concentration from 1M to 10M of precipitation agent in water.
  • Embodiment 16 is the method of any of embodiments 6 to 15, wherein the calcination from step (d) contains heating at a temperature from 250 to 800 °C.
  • Embodiment 17 is a method of using the heterostructured silica catalyst of any of embodiments 1 to 6 in a hydrogenation of carbon monoxide reaction.
  • Embodiment 18 is the method of embodiment 17, wherein the hydrogenation of carbon monoxide reaction includes 0.1 to 5 grams of the heterostructured silica catalyst; a feed stream containing synthesis gas (CO/H2) at a weight hourly space velocity (WHSV) of 1000 to 2500; a temperature of 200 to 500 °C; and a pressure of 0 to 15 bar.
  • Embodiment 19 is the method of embodiment 18, wherein the carbon monoxide conversion is 70 to 78 % at 300 °C, 67 to 80 % at 325 °C, and 14 to 53 % at 350 °C.
  • Embodiment 20 is the method of any of embodiments 17 to 19, further including the step of producing methane, olefins, paraffins, and carbon dioxide, wherein the selectivity of methane is 11 to 28 %, the selectivity of olefins is 24 to 41 %, the selectivity of paraffins is 13 to 21 %, and the selectivity of carbon dioxide is 13 to 41 %, based on a reaction mass balance of 95 ⁇ 5%.
  • FIG. 1 depicts a system for the hydrogenation of carbon monoxide.
  • FIG. 2 is an image showing the physical morphology of a filtered support material having uniform single crystal structure.
  • FIG. 3 is a graph showing the activity/selectivity results of a MHH-SiCh catalyst.
  • the catalysts of the present invention offer a solution to the problems associated with currently available silica supported catalysts.
  • the solution is premised on forming a uniform and uniquely heterostructured S1O2 material (e.g., MHH-S1O2 material) with an active metal, an alkaline earth metal, and silicon (Si) present in the crystal lattice structure.
  • S1O2 material e.g., MHH-S1O2 material
  • Si silicon
  • heterostructured Silica Catalysts [0031] Embodiments herein describe heterostructured silica catalysts and methods of making and using the heterostructured silica catalysts.
  • the catalysts of the present invention can include a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • the catalytically active material used to prepare the heterostructured silica catalysts of the present invention includes one or more catalytically active metals.
  • the crystal lattice structure of the catalyst can contain one metal (i.e., monometallic), two metals (i.e., bimetallic), three metals (i.e., trimetallic), four metals (i.e., tetrametallic) or more metals.
  • the catalytic metal is a transition metal. An amount of transition metal can depend inter alia on the desired activity of the catalyst.
  • Non-limiting examples of transition metal include scandium (Sc), yttrium (Y), lanthanum (La), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt, (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), copper (Cu), silver (Ag), and gold (Au).
  • the transition metal is one or more of iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), zirconium (Zr), or titanium (Ti), with iron (Fe) being preferred.
  • the amount of transition metal comprised in the heterostructured silica catalyst can include 0.01 to 20 wt. % or 0.1 to 10 wt. % and all values and ranges there between.
  • the catalyst can include about 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, or 9.9 wt. % of the transition metal based on the total weight of the catalyst.
  • the heterostructured silica catalysts of the present invention also include an alkaline earth metal oxide.
  • the alkaline earth metal oxide may be inert or be able to participate in catalytic reactions.
  • the alkaline earth metal oxide can be one or more of magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), or strontium (SrO), with magnesium oxide (MgO) being preferred.
  • the amount of alkaline earth metal from the metal oxide thereof comprised in the heterostructured silica catalyst can include 5 to 40 wt.% or 10 to 20 wt.% and all values and ranges there between.
  • the catalyst can include 5, 5.5, 6, 6.5, 7.0, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 1 1.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 30, 30.5, or 40 wt.% based on the total weight of the catalyst.
  • the alkaline earth metal oxide can be present in the crystal lattice structure of the catalyst in a weight ratio of silicon to alkaline earth metal from 0.5: 1 to 5: 1 with 1 : 1 to 3 : 1 and all values and ranges there between (e.g., 1.1 : 1, 1.2: 1, 1.3 : 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2.0: 1, 2.1 : 1, 2.2: 1, 2.3 : 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1).
  • Alkaline earth metal oxides and corresponding derivatives/precursors thereof can be purchased from commercial manufactures such as Sigma- Aldrich®, USA.
  • Silica or silicon dioxide is the oxide of silicon that is highly abundant in nature (e.g., quartz). Silica more so than almost any material, exists in many crystalline forms (e.g., polymorphs). Due to a range of robust structure properties and high surface area, silica is often included in catalyst support materials to which active metals are affixed. Great effort has been made to maximize the surface area of a catalyst by increasing distribution over and within the support.
  • the amount of silicon (Si) from silica comprised in the heterostructured silica catalyst can include 10 to 50 wt. % or 20 to 40 wt.
  • % and all values and ranges there between e.g., 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39 wt.% of silicon, based on the total weight of the catalyst.
  • the sources of silicon can be derived from organic compounds that readily provide soluble sources of silicon in a template reaction.
  • a template reaction is a ligand-based reaction that occurs between two or more adjacent coordination sites on a metal center.
  • the organic source of silicon that be used to form the silica comprised in the heterostructured silica catalysts include tetraalkyl orthosilicates.
  • Tetraalkyl orthosilicate derivatives e.g., tetraethyl orthosilicate (TEOS) can be purchased from commercial manufactures such as Sigma-Aldrich®, USA.
  • the catalysts of the present invention can be prepared by using the following non- limiting steps.
  • orthosilicate can be added to heated aqueous alkaline earth metal salt (e.g., MgCh). Under these conditions, orthosilicate can be converted into polycondensed silica with an external network of alkaline earth metal atoms (e.g., Mg) along with an organic phase (e.g., ethyl moiety).
  • a transition metal salt e.g., iron citrate
  • the transition metal salt dissolves slowly to allow the transition metal (e.g., iron) to network with the existing solution in a regular systematic pattern. This regular patterned solution can then be precipitated by means of precipitating agent to keep the heterostructure intact.
  • interstitial water can be removed producing a uniformly shaped material.
  • Step 1 of the method can include subjecting an aqueous solution comprising an alkaline earth metal precursor and a silicon containing organic template (e.g., tetraalkyl orthosilicate) to conditions sufficient to form polycondensed silica having an external network of alkali earth metal atoms.
  • a silicon containing organic template e.g., tetraalkyl orthosilicate
  • the molar ratio of tetraalkyl orthosilicate to alkaline earth metal precursor can be 0.5 : 1 to 6: 1, preferably 1 : 1 to 4: 1 and all ranges and values there between (e.g., 1.1 : 1, 1.2: 1, 1.3 : 1, 1.4: 1, 1.5 : 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2.0: 1, 2.1 : 1, 2.2: 1, 2.3 : 1, 2.4: 1, 2.5 : 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1, 3.0: 1, 3.1 : 1, 3.2: 1, 3.3 : 1, 3.4: 1, 3.5 : 1, 3.6: 1, 3.7: 1, 3.8: 1, or 3.9: 1).
  • Non-limiting examples of the alkaline earth metal precursor include magnesium fluoride (MgF 2 ), magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), magnesium iodide (Mgl 2 ), calcium fluoride (CaF 2 ), calcium chloride (CaCl 2 ), calcium bromide (CaBr 2 ), calcium iodide (Cab), barium fluoride (BaF 2 ), barium chloride (BaCl 2 ), barium bromide (BaBr 2 ), barium iodide (Bab), strontium fluoride (SrF 2 ), strontium chloride (SrCl 2 ), strontium bromide (SrBr 2 ), strontium iodide (Srb), with MgCl 2 being preferred.
  • MgCl 2 magnesium fluoride
  • MgCl 2 magnesium chloride
  • MgBr 2 magnesium bromide
  • Non-limiting examples of tetraalkyl orthosilicates or alkoxy silanes include tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetrakis(methoxyethoxy)silane, tetrakis(methoxypropoxy)silane, tetrakis(ethoxyethoxy)silane, tetrakis(methoxyethoxyethoxy)silane, trimethoxyethoxysilane, dimethoxydiethoxysilane, triethoxymethoxysilane, tetra-(4-methyl-2-pentoxy)silane, and tetra-(2-ethylhexoxy)silane.
  • TMOS tetramethyl
  • tetrafunctional silanes with acyloxy groups include tetraacetoxyoxysilane, silicon tetrapropionate and silicon tetrabutyrate.
  • the tetraalkyl orthosilicate is TEOS.
  • the aqueous solution can include from 10 to 100 vol.% water and all ranges and values there between (e.g., 10, 20, 30, 40, 50, 60, 70, 80, 90 vol.%)
  • the aqueous solution can also include an alcohol.
  • Non-limiting examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, or glycerol to name a few, preferably the alcohol is ethanol, propanol, butanol, or mixtures thereof.
  • the aqueous solution of alkaline earth metal precursor and an tetraalkyl orthosilicate can be mixed together using suitable mixing equipment and heated to a temperature of room temperature to 90 °C, preferably 50 °C to 60 °C, and all values and ranges there between (e.g., 51, 52, 53, 54, 55, 56, 57, 58, 59 °C).
  • an alkaline earth metal precursor solution can first be formed.
  • the alkaline earth metal precursor solution can be heated to a temperature ranging from room temperature to 95 °C, preferably from 40 to 70 °C and all ranges and values there between (e.g., 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, or 69 °C) followed by adding the tetraalkyl orthosilicate to the solution.
  • a mixture of TEOS and MgCh results in the formation of a polycondensed support material containing uniform single crystal structure including heterostructures of silica magnesia within an organic template.
  • Step 2 of the method can include adding a transition metal precursor material to the aqueous solution including polycondensed silica having an external network of alkali earth metal atoms under conditions to incorporate transition metal atoms into the polycondensed silica.
  • the molar ratio of alkaline earth metal precursor to transition metal precursor can be 5 : 1 to 50: 1, preferably 20: 1 to 30: 1 and all ranges and values there between Non-limiting ratios include about 20.1 : 1, 20.5 : 1, 21.0: 1, 21.5 : 1, 22.0: 1, 22.5 : 1, 23.0: 1, 23.5 : 1, , 24.0: 1, 24.5 : 1, 25.0: 1, 25.5 : 1, 26: 1, 26.5 : 1, 27.0: 1, 27.5 : 1, 28.0: 1, 28.5 : 1, 29.0: 1, 29.5 : 1, or 30: 1.
  • the transition metal precursor can include ferric citrate, nickel citrate, copper citrate, zinc citrate, aluminum citrate, zirconium citrate, or titanium citrate.
  • the aqueous mixture can be stirred (e.g., vigorously) for an appropriate amount of time to incorporate the transition metal precursor.
  • the appropriate amount of time can include from 30 minutes to overnight (e.g., approximately 12 hours), 1 hour to 6 hours, preferably about 2 hours.
  • Step 3 of the method can include forming a solid material from the polycondensed silica.
  • the solid material can be obtained by adding a precipitating agent.
  • the precipitating agent can be one or more of ammonium hydroxide (NH4OH), ammonium carbonate [(NH4)2C03], ammonium bicarbonate (NH4HCO3), sodium carbonate (Na2CCb), potassium carbonate (K2CO3), sodium bicarbonate (NaHCCb), or potassium bicarbonate (KHCO3).
  • the precipitating agent is H4OH.
  • the precipitating agent can have a concentration from 1M to 10M of precipitation agent in water.
  • the aqueous mixture can be stirred (e.g., vigorously) for an appropriate amount of time to form the solid material.
  • the appropriate amount of time can include from 30 minutes to overnight (e.g., approximately 12 hours), 1 hour to 6 hours, preferably about 2 hours.
  • Step 4 of the method can include drying and calcining the solid material to form a heterostructured silica catalyst comprising a transition metal, an alkaline earth metal oxide, and silica, wherein the transition metal, the alkaline earth metal from the metal oxide thereof, and silicon (Si) from silica are each present in the crystal lattice structure of the catalyst.
  • the solid material After the solid material is formed by precipitation, it can be collected by filtration, washed with hot water, and dried overnight at a temperature of 100 to 150 °C, preferably 130 °C.
  • the material can be treated with an oxidant (e.g., H2O2) under stirring conditions for a period of time (e.g., 30 minutes to 2 hours, preferably approximately 1 hour) followed by isolation by filtration and drying.
  • Drying can include a time of 2 hours to overnight, preferably approximately 4 hours at a temperature of 100 to 150 °C, preferably 130 °C.
  • Further calcination of the dried solid material can include heating at a temperature from 250 to 800 °C and all ranges and values there between preferably 400 to 500 °C.
  • calcination is employed under temperature ramping conditions (e.g., 3 °C / minute) to a hold temperature (e.g., 450 °C) and holding for 3 to 7 hours, preferably 5 hours in air to form the final heterostructured silica catalysts.
  • temperature ramping conditions e.g., 3 °C / minute
  • hold temperature e.g., 450 °C
  • the morphology, structure, and quality of the heterostructured silica catalysts of the present invention can be evaluated using techniques, such as, but not limited to, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, UV-VIS, optical reflectivity, optical microscopy, low-energy electron microscopy (LEEM), low-energy diffraction (LEED), atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning tunnelling microscopy (STM), photoelectron microscopy (PES), angle-resolved photoelectron spectroscopy (ARPES), photoemission electron microscope (PEEM), energy dispersive X-ray spectroscopy (EDS, EDX, or XEDS), X-ray photoelectron spectroscopy (XPS), Image J data analysis software, reflection high-energy electron diffraction (RHEED), or microscope-based videography.
  • SEM scanning electron microscopy
  • HRTEM high-resolution
  • the heterostructured silica catalyst of the present invention can be used to catalyze a chemical reaction, such as the hydrogenation of carbon monoxide.
  • the hydrogenation of carbon monoxide includes the conversion of synthesis gas (e.g., gas that include H 2 and CO) to carbon dioxide, methane, olefins (e.g., ethylene, propylene, and butylenes), and and/or paraffins (e.g., C 2 + alkanes).
  • synthesis gas e.g., gas that include H 2 and CO
  • methane olefins
  • olefins e.g., ethylene, propylene, and butylenes
  • paraffins e.g., C 2 + alkanes
  • Conditions sufficient for production include temperature, time, syngas ratio and concentration, space velocity, and pressure.
  • the temperature range for hydrocarbon production may range from about 200 °C to 500 °C, preferably 250 °C to 350 °C.
  • a weighted hourly space velocity (WHSV) of syngas higher than 1000 h "1 can be used, preferably between 1000 and 10,000 h “1 , most preferably approximately 1875 h "1 .
  • the conversion of syngas can be carried out at a pressure from 0 to 15 bar, preferably approximately 5 bar, or at atmospheric pressure.
  • the conditions for hydrocarbon production may be varied based on the type of the reactor.
  • the catalysts Prior to using the heterostructured silica catalyst of the present invention, the catalysts can be activated by ramping 3 °C / minute to 350 °C and holding for 16 hour under 50:50 H 2 /N 2 flow (e.g., WHSV: 3600 h "1 ).
  • the reaction of the methods and system disclosed herein can occur in any type of reactor.
  • reactors include a high throughput fixed bed flow reactor setup housed in a temperature controlled system fitted with regulators to maintain pressure during the reaction. It is also envision the method and systems may also include the ability to regenerate used/deactivated catalyst in a continuous process such as in a fluidized bed reactor.
  • the method and system can further include collecting or storing the produced hydrocarbon product along with using the produced hydrocarbon product to produce downstream petrochemical and/or polymer products. Reaction products of the reactions can be analyzed by online GC analysis for purity.
  • a system 10 which can be used to convert syngas to hydrocarbon products with the heterostructured silica catalysts of the present invention.
  • the system 10 can include a syngas source 11, a reactor 12, and a collection device 13.
  • the syngas source 11 can be configured to be in fluid communication with the reactor 12 via an inlet 17 on the reactor.
  • one or more inlets can be present that can deliver syngas in a single feed as a H2/CO mixture or separately via multiple inlets (not shown).
  • the syngas source can be configured such that it regulates the amount of syngas feed entering the reactor 12.
  • the reactor 12 can include a reaction zone 18 having the heterostructured silica catalyst 14 of the present invention (MHH-S1O2 catalyst).
  • the amounts of the syngas feed 11 and the catalyst 14 used can be modified as desired to achieve a given amount of product produced by the system 10.
  • the reactor 12 can include an outlet 15 for products produced in the reaction zone 18.
  • the products produced can include carbon dioxide, methane, olefins ⁇ e.g., ethylene, propylene, and butylenes), and/or paraffins ⁇ e.g., C2+ alkanes).
  • the collection device 13 can be in fluid communication with the reactor 12 via the outlet 15. Both the inlet 17 and the outlet 15 can be open and closed as desired.
  • the collection device 13 can be configured to store, further process, or transfer desired reaction products ⁇ e.g., olefins) for other uses.
  • the system 10 can also include a heating source 16.
  • the heating source 16 can be configured to heat the reaction zone 18 to a temperature sufficient ⁇ e.g., 250 to 350 °C) to convert syngas to hydrocarbon products.
  • a non-limiting example of a heating source 16 can be a temperature controlled furnace.
  • any unreacted syngas can be recycled and included in the syngas feed to further maximize the overall conversion of syngas to hydrocarbon products.
  • certain products can be separated by known processes in the art and used in other processes to produce commercially valuable chemicals. This increases the efficiency and commercial value of the syngas conversion process of the present invention.
  • Carbon monoxide (CO) gas and hydrogen (H2) gas can be obtained from various sources.
  • the CO can be obtained from streams coming from other chemical processes, like partial oxidation of carbon-containing compounds, iron smelting, photochemical process, syngas production, reforming reactions, and/or various forms of combustion.
  • Fh can be obtain from streams coming from other chemical processes, like water splitting ⁇ e.g., photocatalysis, electrolysis, or the like), syngas production, ethane cracking, methanol synthesis, or conversion of methane to aromatics.
  • the molar ratio of H2/CO in the reactant stream can be 1 or more. In some embodiments, the H2/CO molar ratio can be from 1 to 10, preferably approximately 2.
  • the remainder of the reactant gas stream can include another gas or gases provided the gas or gases are inert, such as argon (Ar), nitrogen (N2), or methane and further provided that they do not negatively affect the reaction. All possible percentages of CO plus H2 plus inert gas in the current embodiments can have the described H2/CO ratios herein.
  • the reactant mixture is highly pure and devoid of water or steam.
  • the feed gases can be dried prior to use (e.g., pass through a drying media) or contain a minimal amount of water or no water at all.
  • the process of the present invention can produce a product stream that includes a mixture of carbon dioxide, methane, olefins (e.g., ethylene, propylene, and butylenes), and/or paraffins (e.g., C2+ alkanes).
  • the carbon monoxide conversion can be 70 to 78% at 300 °C, 67 to 80% at 325 °C, and 14 to 53% at 350 °C.
  • the selectivity of methane can be 1 1 to 28 %
  • the selectivity of olefins can be 24 to 41%
  • the selectivity of paraffins can be 13 to 21%
  • the selectivity of carbon dioxide can be 13 to 41%, based on a reaction mass balance of 95 ⁇ 5%.
  • Aqueous magnesium chloride (1M), tetraethyl orthosilicate (98%, TEOS), ferric citrate (16.5 to 18.5 wt%, based on total weight of solution), aqueous ammonium hydroxide (1M, 3M, 5M, and 7M), and aqueous hydrogen peroxide (15%) were used without further purification.
  • the material was immersed in H 2 0 2 (15 %, 50 ml) for 1 hour followed by filtration and drying for 4 hours at 130 °C. The material was then calcined ramping 3 °C / minute to 450 °C and holding for 5 hours in air before use as support in catalyst preparations.
  • FIG. 2 depicts an photograph of the catalyst on a filtered support material.
  • the catalyst of the present invention had a uniform single crystal structure.
  • Crystals 20 were determined to be heterostructures of silica magnesia having an organic template. Without wishing to be bound by theory, it is believed that once the active metal deposits on the crystals, the organic template dissolved, allowing the metal to reach the support center having systematic pattern to obtain a uniformly designed supported metal catalyst. Elemental composition of the samples determined by EDX are shown in Table 1.
  • Catalysts were tested for activity, selectivity, as well as short term and long term stability. Prior to activity testing, catalysts were activated by ramping 3 °C / minute to 350 °C and holding for 16 hour under 50:50 H2/N2 flow (WHSV: 3600 h "1 ). Catalytic evaluation was carried out in a high throughput fixed bed flow reactor setup housed in a temperature controlled system fitted with regulators to maintain pressure during the reaction. The products of the reactions were analyzed by online GC analysis. The evaluation was carried out under the following conditions unless otherwise mentioned elsewhere; 5 bar, WHSV: 1875 h "1 , H2/CO ratio of 2. The mass balance of the reactions is calculated to be 95 ⁇ 5 %. FIG.
  • Example 3 depicts a temperature scan of the catalyst of Example 3 for the activity/selectivity evaluation.
  • the exploded view shows which bars represent carbon dioxide 30, methane 31, olefins 32, and paraffins 33 conversion/selectivity data points for each measurement.
  • Carbon monoxide conversion 34 and temperature 35 data points are shown as line graphs. The graph showed the variation in conversion and product selectivities over a duration of 603 hours.
  • the catalyst of Example 3 showed low conversion at low temperature and increased conversion as temperature increased to a maximum at 350 °C. On lowering the temperature, the conversion drop was not observed until 300 °C, which remains near 80%. Further decrease in temperature produced the usual effect of a conversion drop to 25% at 245 °C.
  • Table 2 The results of FIG. 3 are tabulated in Table 2.
  • materials can have applications in wide variety of industries that use silica as a support material for catalysts.

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Abstract

L'invention concerne des catalyseurs de silice hétérostructurée (silice hétérostructurée Haider modifiée) et des procédés d'utilisation et de préparation de ceux-ci. Les catalyseurs de silice hétérostructurée comprennent un métal de transition, un oxyde de métal alcalino-terreux et de la silice. Le métal de transition, le métal alcalino-terreux à partir de l'oxyde métallique de celui-ci, et le silicium (Si) à partir de la silice sont chacun présents dans la structure de réseau cristallin du catalyseur. Le catalyseur peut être utilisé dans, par exemple, l'hydrogénation de monoxyde de carbone.
PCT/IB2017/057956 2016-12-15 2017-12-14 Matériaux de silice modifiés de nouvelle génération pour des performances catalytiques accrues et des applications industrielles WO2018109718A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019234631A1 (fr) * 2018-06-05 2019-12-12 Sabic Global Technologies B.V. Catalyseurs hétérogènes à base de métaux de transition cristallins de métal massifs, leurs procédés de fabrication et leurs utilisations
CN110893339A (zh) * 2018-09-12 2020-03-20 华东理工大学 一种钼基耐硫甲烷化催化剂及其制备方法与应用
CN110988005A (zh) * 2019-12-17 2020-04-10 中国科学技术大学 一种真空系统下磁化材料的强永磁体装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5019293A (en) 1989-06-12 1991-05-28 Cornell Research Foundation, Inc. Use of hydrogen peroxide in preparing magnesium containing silicate sols for coating and fiber formation
US5153031A (en) 1989-06-12 1992-10-06 Cornell Research Foundation, Inc. Use of hydrogen peroxide in preparing magnesium containing silicate sols for coating and fiber formation
US20040106517A1 (en) * 2000-05-23 2004-06-03 Dlamini Thulani Humphrey Chemicals from synthesis gas
US20090111684A1 (en) * 2007-08-30 2009-04-30 Rentech, Inc. Method for activating strengthened iron catalyst for slurry reactors

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556725A (en) 1969-02-26 1971-01-19 Sylvania Electric Prod Process for producing low-bulk density silica
JPS60202742A (ja) * 1984-03-26 1985-10-14 Matsushita Electric Ind Co Ltd 触媒燃焼用酸化触媒体
US4952544A (en) * 1987-03-05 1990-08-28 Uop Stable intercalated clays and preparation method
CN100355496C (zh) * 2003-12-10 2007-12-19 浙江工业大学 氧化亚铁Fe1－xO在制备F－T合成熔铁催化剂中的应用
JP4503444B2 (ja) * 2004-02-05 2010-07-14 ダイヤニトリックス株式会社 アクリロニトリル製造用触媒、及びアクリロニトリルの製造方法
JP2013014451A (ja) * 2011-07-01 2013-01-24 National Institute Of Advanced Industrial Science & Technology ジルコニア系メソ多孔性複合酸化物粒子及びその製造方法
WO2016011240A1 (fr) * 2014-07-17 2016-01-21 Sabic Global Technologies B.V. Utilisation de catalyseurs d'olivine pour reformage de méthane à l'aide de dioxyde de carbone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5019293A (en) 1989-06-12 1991-05-28 Cornell Research Foundation, Inc. Use of hydrogen peroxide in preparing magnesium containing silicate sols for coating and fiber formation
US5153031A (en) 1989-06-12 1992-10-06 Cornell Research Foundation, Inc. Use of hydrogen peroxide in preparing magnesium containing silicate sols for coating and fiber formation
US20040106517A1 (en) * 2000-05-23 2004-06-03 Dlamini Thulani Humphrey Chemicals from synthesis gas
US20090111684A1 (en) * 2007-08-30 2009-04-30 Rentech, Inc. Method for activating strengthened iron catalyst for slurry reactors

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KANDIS SUDSAKORN ET AL: "Preparation of Attrition-Resistant Spray-Dried Fe Fischer-Tropsch Catalysts Using Precipitated SiO 2", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 40, no. 22, 1 October 2001 (2001-10-01), pages 4778 - 4784, XP055021184, ISSN: 0888-5885, DOI: 10.1021/ie0101442 *
LIU ET AL.: "Calcein-functionalized Fe 0 Si0 nanoparticles as a reusable fluorescent nanoprobe for copper(II) ion", MICROCHIM ACTA, vol. 182, 2015, pages 547 - 555, XP035429644, DOI: doi:10.1007/s00604-014-1358-7

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019234631A1 (fr) * 2018-06-05 2019-12-12 Sabic Global Technologies B.V. Catalyseurs hétérogènes à base de métaux de transition cristallins de métal massifs, leurs procédés de fabrication et leurs utilisations
CN110893339A (zh) * 2018-09-12 2020-03-20 华东理工大学 一种钼基耐硫甲烷化催化剂及其制备方法与应用
CN110988005A (zh) * 2019-12-17 2020-04-10 中国科学技术大学 一种真空系统下磁化材料的强永磁体装置

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